Pesticidal aminomethylheterocyclic compounds

ABSTRACT

Fungicidally active compounds of the formula ##STR1## in which X represents oxygen or sulphur, 
     R represents cycloalkyl, or represents optionally substituted aryl, or represents the radical ##STR2## R 1  and R 2  each independently is hydrogen or an organic radical, or together with the nitrogen atom form a heterocyclic radical, 
     R 3  represents hydrogen, alkyl or optionally substituted aryl, and 
     R 4  represents alkyl or cycloalkyl, or represents optionally substituted aryl, 
     but wherein R 3  and R 4  may not simultaneously represent methyl, 
     and acid addition salts thereof, as well as intermediates therefor.

The invention relates to new aminomethylheterocyclic compounds, severalprocesses for their preparation, their use in agents for combating pestsand new intermediate products.

It is known that certain aminomethyldioxolanes, such as, for example,the compound 2-isobutyl-2-methyl-4-(1-piperi-dinylmethyl)-1,3-dioxolaneor the compound 2-methyl-2-nonyl-4-di-n-butylaminomethyl-1,3-dioxolaneor the compound2-(2-cyclohexylmethyl-2-propyl)-2-methyl-4-(1-piperidinyl-methyl)-1,3-dioxolaneor the compound 2-(2-cyclohexyl-methyl-2-propyl)-2-methyl-4-(1-perhydroazepinylmethyl)-1,3dioxolane, have fungicidalproperties (compare, for example, EP 97,822).

However, the activity of these already known compounds is not completelysatisfactory in all fields of use, especially when low amounts areapplied and in the case of low concentrations. Newaminomethylheterocyclic compounds of the general formula (I) ##STR3## inwhich X represents oxygen or sulphur,

R represents cycloalkyl, or represents optionally substituted aryl, orrepresents a radical ##STR4## R¹ and R² independently of one anothereach represent hydrogen, alkyl, alkenyl, alkinyl, alkoxyalkyl,dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, alkoxycarbonylalkyl,dioxolanylalkyl, dioxanylalkyl or oxolanylalkyl, or represent in eachcase optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl,aralkenyl or aryl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent an optionally substituted saturated heterocyclic radical,which can optionally contain further hetero atoms, and

R³ represents hydrogen, alkyl or optionally substituted aryl and

R⁴ represents alkyl or cycloalkyl, or represents optionally substitutedaryl, but wherein R3 and R4 may not simultaneously represent methyl,

and acid addition salts thereof, have been found.

The compounds of the formula (I) can exist as geometric and/or opticalisomers or isomer mixtures of varying composition. Both the pure isomersand the isomer mixtures are claimed according to the invention whencompounds of the formula (I) are referred to.

It has furthermore been found that the new aminomethylheterocycliccompounds of the general formula (I) ##STR5## in which X representsoxygen or sulphur,

R represents cycloalkyl, or represents optionally substituted aryl, orrepresents a radical ##STR6## R³ represents hydrogen, alkyl oroptionally substituted aryl and R⁴ represents alkyl or cycloalkyl, orrepresents optionally substituted aryl,

but wherein R³ and R⁴ may not simultaneously represent methyl,

R¹ and R² independently of one another each represent hydrogen, alkyl,alkenyl, alkinyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl,hydroxyalkoxyalkyl, alkoxycarbonylalkyl, dioxolanylalkyl, dioxanylalkylor oxolanylalkyl, or represent in each case optionally substitutedcycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent an optionally substituted saturated heterocyclic radical,which can optionally contain further hetero atoms,

and acid addition salts thereof, are obtained by a process in which

(a) substituted heterocyclic compounds of the formula (II) ##STR7## inwhich R and X have the abovementioned meanings and

E¹ represents an electron-withdrawing leaving group, are reacted withamines of the formula (III) ##STR8## in which R¹ and R² have theabovementioned meanings, if appropriate in the presence of a diluent andif appropriate in the presence of an acid-binding agent, or by a processin which

(b) the aminomethylheterocyclic compounds obtainable by process (a), ofthe formula (Ia) ##STR9## in which R, R¹ and X have the abovementionedmeanings,

are reacted with alkylating agents of the formula (IV)

    R.sup.2-1 --E.sup.2                                        (IV)

in which

R²⁻¹ represents alkyl, alkenyl, alkinyl, alkoxyalkyl, dialkoxyalkyl,hydroxyalkyl, hydroxyalkoxyalkyl, alkoxycarbonylalkyl, dioxolanylalkyl,dioxapylalkyl or oxolanylalkyl, or represents in each case optionallysubstituted cycloalkylalkyl, cycloalkyl, aralkyl or aralkenyl and

E² represents an electron-withdrawing leaving group,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent, and, if appropriate, an acid is thenadded on or the reaction is followed by a physical resolution method.

Finally, it has been found that the new aminomethylheterocycliccompounds of the general formula (I) have an action against pests, inparticular against fungal pests.

Surprisingly, the aminomethylheterocyclic compounds of the generalformula (I) according to the invention inter alia exhibit a betterfungicidal activity than the aminomethyldioxolanes known from the priorart, such as, for example, the compound2-isobutyl-2-methyl-4-(1-piperidinylmethyl)1,3-dioxolane or the compound2-methyl-2-nonyl-4-di-n-butyl-aminomethyl-1,3-dioxolane or the compound2-(2-cyclohexyl-2-methyl(2-propyl)-2-methyl-4-(1-piperidinylmethyl)-1,3dioxolane or the compound2-(2-cyclohexylmethyl-2-propyl)2-methyl4-(1-perhydroazepinylmethyl)-1,3-dioxolane, which are closely relatedcompounds chemically and from the point of view of their action.

Formula (I) provides a general definition of the aminomethylheterocycliccompounds according to the invention. Preferred compounds of the formula(I) are those in which

X represents oxygen or sulphur,

R represents cycloalkyl having 3 to 7 carbon atoms, or represents arylwhich has 6 to 10 carbon atoms and is optionally substituted by one ormore identical or different straight-chain or branched alkyl radicalshaving 1 to 12 carbon atoms, or represents a radical ##STR10## R¹ and R²independently of one another each represent hydrogen, or represent ineach case straightchain or branched alkyl having 1 to 12 carbon atoms,alkenyl having 3 to 8 carbon atoms, alkinyl having 3 to 8 carbon atoms,hydroxyalkyl having 2 to 6 carbon atoms, alkoxyalkyl or dialkoxyalkylhaving in each case 1 to 6 carbon atoms or hydroxyalkoxyalkyl having 2to 6 carbon atoms in the individual alkyl parts, or representalkoxycarbonylalkyl having 1 to 6 carbon atoms per alkoxy and alkylpart, or represent in each case straight-chain or brancheddioxolanylalkyl, dioxanylalkyl or oxolanylalkyl having in each case 1 to4 carbon atoms in the alkyl part, or represent cycloalkyl orcycloalkylalkyl having in each case 3 to 7 carbon atoms in thecycloalkyl part and if appropriate 1 to 4 carbon atoms in thestraight-chain or branched alkyl part and in each case optionallysubstituted in the cycloalkyl part by one or more identical or differentsubstituents, possible substituents in each case being: halogen and ineach case straight-chain or branched alkyl, alkoxy, halogenoalkyl andhalogenoalkoxy having in each case 1 to 4 carbon atoms and ifappropriate 1 to 9 identical or different halogen atoms; or in additionrepresent arylalkyl, arylalkenyl or aryl having in each case 6 to 10carbon atoms in the aryl part and if appropriate up to 6 carbon atoms inthe straight-chain or branched alkyl or alkenyl part and in each caseoptionally substituted in the aryl part by one or more identical ordifferent substituents, possible substituents on the aryl in each casebeing: halogen, cyano, nitro and in each case straightchain or branchedalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy,halogenoalkylthio, alkoxycarbonyl and alkoximinoalkyl having in eachcase 1 to 4 carbon atoms in the individual alkyl parts and ifappropriate 1 to 9 identical or different halogen atoms, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a saturated 5- to 7-membered heterocyclic radical which isoptionally substituted by one or more identical or differentsubstituents and can optionally contain a further hetero atom, inparticular nitrogen, oxygen or sulphur, possible substituents being: ineach case straight-chain or branched alkyl or hydroxyalkyl having ineach case 1 to 4 carbon atoms,

R³ represents hydrogen, or represents straight-chain or branched alkylhaving 1 to 12 carbon atoms, or represents aryl which has 6 to 10 carbonatoms and is optionally substituted by one or more identical ordifferent straight-chain or branched alkyl radicals having 1 to 12carbon atoms and

R⁴ represents straight-chain or branched alkyl having 1 to 12 carbonatoms, or represents cycloalkyl having 3 to 7 carbon atoms, orrepresents aryl which has 6 to 10 carbon atoms and is optionallysubstituted by one or more identical or different straight-chain orbranched alkyl radicals having 1 to 12 carbon atoms,

but wherein R³ and R⁴ may not simultaneously represent methyl.

Particularly preferred compounds of the formula (I) are those in which

X represents oxygen or sulphur:

R represents cyclopentyl or cyclohexyl, or represents phenyl which isoptionally substituted by one to three identical or differentsubstituents from the group comprising methyl, ethyl, n- or i-propyl andn-, i-, s- or t-butyl, or represents a radical ##STR11## R¹ and R²independently of one another each represent hydro

gen methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl,n- or i-hexyl, n- or i-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n-or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl,methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl,ethoxypropyl, propoxypropyl, butoxypropyl, hydroxyethoxyethyl,dimethoxyethyl, dimethoxypropyl, diethoxyethyl, methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl,propoxycarbonylethyl, propoxycarbonylpropyl, dioxolanylmethyl,dioxolanylethyl, dioxanylmethyl, dioxanylethyl, oxolanylmethyl oroxolanylethyl, or represent cyclopropyl, cyclopropylmethyl,cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl,cyclohexyl or cyclohexylmethyl, in each case optionally substituted byone to five identical or different substituents from the groupcomprising fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,n-, i-, s- or t-butyl, trifluoromethyl and trifluoromethoxy, orrepresent phenyl, benzyl or phenethyl, in each case optionallysubstituted by one to three identical or different substituents,possible substituents in each case being: fluorine, chlorine, bromine,cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl ormethoximinomethyl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula ##STR12## which isoptionally substituted by one to three identical or differentsubstituents, possible substituents in each case being: methyl, ethyland hydroxymethyl,

and

R³ represents hydrogen, methyl, ethyl or n- or i-propyl, or representsin each case straight-chain or branched butyl, pentyl or hexyl, orrepresents phenyl which is optionally substituted by one to threeidentical or different substituents from the group comprising methyl,ethyl, n- or i-propyl and n-, i-, s- or t-butyl and

R⁴ represents methyl, ethyl or n- or i-propyl, or represents in eachcase straight-chain or branched butyl, pentyl or hexyl, or repre$entscyclopentyl or cyclohexyl, or represents phenyl which is optionallysubstituted by one to three identical or different subtituents from thegroup comprising methyl, ethyl, n-or i-propyl and n-, i-, s- or t-butyl,

but wherein R³ and R⁴ may not simultaneously represent methyl.

Especially preferred compounds of the formula (I) are those in which

X represents oxygen or sulphur,

R represents cyclohexyl, or represents phenyl, or represents a radical##STR13## R¹ and R² independently of one another each representhydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- ori-pentyl, n- or i-hexyl, allyl, nor i-butenyl, n- or i-pentenyl,propargyl, n- or ibutinyl, hydroxyethyl, hydroxypropyl, methoxyethyl,methoxypropyl, ethoxyethyl, ethoxypropyl, hydroxyethoxyethyl,dimethoxyethyl, diethoxyethyl, methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl,propoxycarbonylethyl, propoxycarbonylpropyl, dioxolanylmethyl,dioxolanylethyl, dioxanylmethyl, oxolanylmethyl, oxolanylethyl,cyclopropylmethyl, dichlorocyclopropylmethyl, dimethylcyclopropylmethyl,dichlorodimethylcyclopropylmethyl, cyclopentyl, cyclhexyl orcyclohexylmethyl or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula ##STR14## which isoptionally substituted by one to three identical or differentsubstituents, possible substituents in each case being: methyl, ethyland hydroxymethyl, and

R³ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl or phenyl and

R⁴ represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, orrepresents cyclohexyl, or represents phenyl,

but wherein R³ and R⁴ may not simultaneously represent methyl.

Addition products of acids and those aminomethylheterocyclic compoundsof the formula (I) in which the substituents X, R, R¹ and R² have themeanings which have already been mentioned for these substituents arealso preferred compounds according to the invention.

The acids which can be added on include, preferably hydrogen halideacids, such as, for example, hydrochloric acid and hydrobromic acid, inparticular hydrochloric acid, and furthermore phosphoric acid, nitricacid, mono-, bi- and trifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, and sulphonic acids, such asp-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid, andfurthermore saccharin.

The following aminomethylheterocyclic compounds of the general formula(I) may be mentioned specifically, in addition to the compoundsmentioned in the preparation examples:

    ______________________________________                                         ##STR15##                     (I)                                             R            X                                                                                     ##STR16##                                               ______________________________________                                         ##STR17##   O                                                                                      ##STR18##                                                ##STR19##   O                                                                                      ##STR20##                                                ##STR21##   O                                                                                      ##STR22##                                                ##STR23##   O                                                                                      ##STR24##                                                ##STR25##   O                                                                                      ##STR26##                                                ##STR27##   O                                                                                      ##STR28##                                                ##STR29##   O                                                                                      ##STR30##                                                ##STR31##   O                                                                                      ##STR32##                                                ##STR33##   S                                                                                      ##STR34##                                                ##STR35##   S                                                                                      ##STR36##                                                ##STR37##   O                                                                                      ##STR38##                                               ______________________________________                                    

If, for example, 8-s-butyl-2-chloromethyl-1,4-dioxaspiro[4,5] decane andpiperidine are used as starting substances, the course of the reactionin process (a) according to the invention can be represented by thefollowign equation: ##STR39##

If, for example, 8-cyclohexyl-2-methylaminomethyl-1,4-dioxaspiro[4,5]decane and allyl bromide are used as starting substances, the course ofthe reaction in process (b) according to the invention can berepresented by the following equation: ##STR40##

Formula (II) provides a general definition of the substitutedhetrocyclic compunds required as starting substances for carrying outprocess (a) according to the invention. In this formula (II), R and Xpreferably represent those radicals which have already mentioned forthese substituents in connection with the descrition of the substancesof the formula (I) according to the invention.

E¹ preferably represents halogen, in particular iodine, chlorine orbromine, or represents alkylsulphoyloxy which is optionally substitutedby halogen, such as fluorine, chlorine, bromine or iodine, or representsarylsulphonyloxy which is optionally substituted, inter alia, by alkylhaving 1 to 4 carbon atoms, such as, for example, methanesulphonyloxy,trifluoro-methanesulphonyloxy or p-toluenesulphonyloxy.

The substituted heterocyclic compounds of the formula (II) are new andthe invention likewise relates to them. They are obtained by a processin which cyclohexanone derivatives of the formula (V) ##STR41## in whichR has the abovementioned meaning,

are cyclized with alcohols of the formula (VI) ##STR42## in which X hasthe abovementioned meaning and

E³ represents halogen or hydroxyl,

if appropriate in the presence of a diluent, such as, for example,toluene, and if appropriate in the presence of an acid catalyst, suchas, for example, p-toluenesulphonic acid, at temperatures between 40° C.and 150° C., and, if appropriate, in the cases where E³ in formula (VI)represents a hydroxyl group, the hydroxymethylheterocyclic compoundsthus obtainable, of the formula (VII) ##STR43## in which X and R havethe abovementioned meanings,

and are reacted in a second stage with optionally substituted alkyl- orarylsulphonyl halides of the formula (VIII)

    Z--SO.sub.2 --Hal                                          (VIII)

in which

Hal represents halogen, in particular chlorine, and

Z represents alkyl which is in each case optionally substituted byhalogen, such as fluorine, chlorine, bromine or iodine, or representsaryl which is optionally substituted by alkyl having 1 to 4 carbonatoms, such as, in particular, methyl, trifluoromethyl or4-methylphenyl,

if appropriate in the presence of a diluent, such as, for example,diethyl ether, and if appropriate in the presence of an acid-bindingagent, such as, for example, pyridine or triethylamine, at temperaturesbetween -20° C. and +100° C.

The geometric isomers thereby obtainable can either be further reactedas mixtures in process (a) according to the invention or resolved bycustomary resolution methods (chromatography or crystallization).

The cyclohexanone derivatives of the formula (V) are known or can beprepared by processes analogous to known processes (compare, forexample, Tetrahedron Letters 28, 2347-2350 [1987]; Tetrahedron Lett. 27,2875-2878 [1986]; Tetrahedron Lett. 1979, 3209-3212; J. Am. chem. Soc.109, 6887-6889 [1987]; J. Am. chem. Soc. 95, 3646-3651 [1973]; J. Am.chem. Soc. 94, 7599-7600 [1972]; Bull. chem. Soc. Jap. 60, 1721-1726[1987]; Chem. Lett. 1986, 1593-1596; Synth. Commun. 15, 759-764[1985];Synth. Commun. 12, 267-277[1982]; J. chem. Soc. chem. Commun. 1984,762-763; J. org. Chem. 38, 1775-1776 [1973]; U.S. Pat. No. 4,251,398;U.S. Pat. No. 3,960,961; preparation examples).

The alcohols of the formula (VI) and the sulphonyl halides of theformula (VIII) are generally known compounds of organic chemistry.

Formula (III) provides a general definition of the amines furthermorerequired as starting substances for carrying out process (a) accordingto the invention. In this formula (III), R¹ and R² preferably representthose radicals which have already been mentioned for these substituentsin connection with the description of the substances of the formula (I)according to the invention.

The amines of the formula (III) are generally known compounds of organicchemistry.

Formula (Ia) provides a general definition of theaminomethylheterocyclic compounds required as starting substances forcarrying out process (b) according to the invention. In this formula(Ia), X, R and R¹ preferably represent those radicals which have alreadybeen mentioned for these substituents in connection with the descriptionof the substances of the formula (I) according to the invention.

The aminomethylheterocyclic compounds of the formula (Ia) are compoundsaccording to the invention and are obtainable with the aid of process(a) according to the invention.

Formula (IV) provides a general definition of the alkylating agentsfurthermore required as starting substances for carrying out process (b)according to the invention. In this formula (IV), R²⁻¹ preferablyrepresents in each case straight-chain or branched alkyl having 1 to 12carbon atoms, alkenyl having 3 to 8 carbon atoms, alkinyl having 3 to 8carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms orhydroxyalkoxyalkyl having 2 to 6 carbon atoms in the individual alkylparts, or represents alkoxycarbonylalkyl having 1 to 6 carbon atoms peralkoxy and alkyl part, or represents in each case straight-chain orbranched dioxolanylalkyl, dioxanylalkyl or oxolanylalkyl having in eachcase 1 to 4 carbon atoms in the alkyl part, or represents cycloalkyl orcycloalkylalkyl having in each case 3 to 7 carbon atoms in thecycloalkyl part and if appropriate 1 to 4 carbon atoms in thestraight-chain or branched alkyl part and in each case optionallysubstituted in the cycloalkyl part by one or more identical or differentsubstituents, possible substituents in each case being: halogenhalogenoalkyl and halogenoalkoxy having in each case 1 to 4 carbon atomsand if appropriate 1 to 9 identical or different halogen atoms; orfurthermore represents arylalkyl or arylalkenyl having in each case 6 to10 carbon atoms in the aryl part and up to 6 carbon atoms in thestraight-chain or branched alkyl or alkenyl part and in each caseoptionally substituted in the aryl part by one or more identical ordifferent substituents, possible substituents on the aryl in each casebeing: halogen, cyano, nitro and in each case straight-chain or branchedalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy,halogenoalkylthio, alkoxycarbonyl and alkoximinoalkyl having in eachcase 1 to 4 carbon atoms in the individual alkyl parts and ifappropriate 1 to 9 identical or different halogen atoms.

R² ²⁻¹ particularly preferably represents methyl, ethyl, n-or i-propyl,n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n-or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- ori-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl,propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl,butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl,diethoxyethyl, methoxycarbonylmethyl, methoxycarbonylethyl,methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl,ethoxycarbonylpropyl, propoxycarbonylmethyl, propoxycarbonylethyl,dioxolanylmethyl, dioxolanylethyl, dioxanylmethyl, dioxanylethyl,oxolanylmethyl or oxolanylethyl, or represents cyclopropyl,cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl,cyclopentylmethyl, substituted by one to five identical or differentsubstituents from the group comprising fluorine, chlorine, bromine,methyl, ethyl, n- or i-propyl, n-, i-, s- and/or t-butyl,trifluoromethyl or trifluoromethoxy, or represents benzyl or phenethyl,in each case optionally substituted by one to three identical ordifferent substituents, possible substituents in each case being:fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl,ethoxycarbonyl and methoximinomethyl.

R²⁻¹ particularly preferably represents methyl, ethyl, n-or or i-propyl,n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, n- ori-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl,hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl,hydroxyethoxyethyl, dimethoxyethyl, diethoxyethyl, methoxycarbonylethyl,methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl,ethoxycarbonylpropyl, propoxyrarbonylmethyl, propoxycarbonylethyl,propoxycarbonylpropyl, dioxolanylmethyl, dioxolanylethyl,dioxanylmethyl, cyclopropylmethyl, oxolanylmethyl, oxolanylethyl,dichlorocyclopropylmethyl, dimethylcyclopropylmethyl,dichlorodimethylcyclopropylmethyl, cyclopentyl, cylohexyl orcyclohexylmethyl.

E² preferably represents halogen, in particular chlorine, bromine oriodine, or represents alkylsulphonyloxy or alkoxysulphonyloxy having ineach case 1 to 4 carbon atoms and in each case optionally substituted byhalogen, such as fluorine, chlorine, bromine or iodine, or representsarylsulphonyloxy which is optionally substituted by, for example, alkylhaving 1 to 4 carbon atoms, such as, for example, methanesulphonyloxy,methoxysulphonyloxy or p-toluenesulphonyloxy.

The alkylating agents of the formula (IV) are likewise generally knowncompounds of organic chemistry or are obtainable by processes analogousto generally known processes.

Possible diluents for carrying out processes (a) and (b) according tothe invention are inert organic solvents or aqueous systems. Theseinclude, in particular, aliphatic or aromatic optionally halogenatedhydrocarbons, such as, for example, benzine, benzene, toluene, xylene,chlorobenzene, petroleum ether, hexane, cyclohexane, methylene chloride,chloroform and carbon tetrachloride, and ethers, such as diethyl ether,dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether;ketones, such as acetone or butanone; nitriles, such as acetonitrile orpropionitrile; amides, such as dimethylformamide, dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acidtriamide; esters, such as ethyl acetate; sulphoxides, such as dimethylsulphoxide, or alcohols, such as methanol, ethanol or propanol.

If appropriate, processes (a) and (b) according to the invention canalso be carried out in a two-phase system, such as, for example,water/toluene or water/methylene chloride, if appropriate in thepresence of a phase transfer catalyst. Examples which may be mentionedof such catalysts are: tetrabutylammonium iodide, tetrabutylammoniumbromide, tributyl-methylphosphonium bromide, trimethyl-C₁₃ /C₁₅-alkylammonium chloride, dibenzyldimethylammonium methyl sulphate,dimethyl-C₁₂ /C₁₄ -alkyl-benzylammonium chloride, tetrabutylammoniumhydroxide, 15-crown-5, 18-crown-6, triethylbenzylammonium chloride andtrimethylbenzylammonium chloride. It is also possible for processes (a)and (b) according to the invention to be carried out without theaddition of a solvent.

Possible acid-binding agents for carrying out processes () and (b)according to the invention are all the inorganic and organic bases whichcan usually be employed. Bases which are preferably used are alkalimetal hydroxides, alcoholates, carbonates or bicarbonates, such as, forexample, sodium hydroxide, sodium methylate, sodium ethylate, sodiumcarbonate or sodium bicarbonate, and also tertiary amines, such as, forexample, triethylamine, N,N-dimethylaniline, pyridine,4-(N,N-dimethylamino)-pyridine, diazabicyclooctane (DABCO),diazabicyclononen (DBN) or diazabicycloundecene (DBU).

It is also possible for the amines of the formulae (III) or (Ia) used asparticipants in the reaction to be employed simultaneously in acorresponding excess as the acidbinding agents.

The reaction temperatures can be varied within a substantial range incarrying out processes (a) and (b) according to the invention. Thereaction is in general carried out at temperatures between +20° C. and+200° C., preferably at temperatures between 80° C. and +180° C.

Processes (a) and (b) according to the invention are in general carriedout under normal pressure. However, it is also possible to applyincreased pressure in the range between 1 and 10 atmospheres. Theprocedure under increased pressure is particularly advisable if one ormore of the participants in the reaction is in gaseous form under normalpressure at the required reaction temperature.

For carrying out process (a) according to the invention, if appropriate0.1 to 1.0 mol of phase transfer catalyst are employed per mol ofsubstituted heterocyclic compound of the formula (II).

For carrying out process (b) according to the invention, in general 1.0to 5.0 mol,preferably 1.0, to 2.0 mols,of alkylating agent of theformula (IV) and 1.0 to 5.0 mols, preferably 1.0 to 2.0 mols,ofacid-binding agent and if appropriate 0.1 to 1.0 mol of phase transfercatalyst are employed per mol of aminomethylheterocyclic compound of theformula (Ia).

In both cases, the reaction is carried out and the reaction products ofthe formula (I) are worked up and isolated by customary methods.

The acid addition salts, which are tolerated by plants, of the compoundsof the formula (I) can be obtained in a simple manner by customary saltformation methods, such as, for example, by dissolving a compound of theformula (I) in a suitable inert solvent and adding the acid, such as,for example, hydrochloric acid, and they can be isolated in a knownmanner, for example by filtration, and if appropriate purified bywashing with an inert organic solvent.

The active compounds according to the invention exhibit a potent actionagainst pests and can be used in practice for combating undesirableharmful organisms. The active compounds are suitable for use as plantprotection agents, in particular as fungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation: Pythium species, such as, for example, Pythium ultimum;Phytophthora species, such as, for example, Phytophthora infestans;Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis; Plasmopara species, such as, forexample, Plasmopara viticola; Per-onospora species, such as, forexample, Peronospora pisi or P. brassicae; Erysiphe species, such as,for example, Erysiphe graminis; Sphaerotheca species, such as, forexample, Sphaerotheca fuliginea; Podosphaera species, such as, forexample, Podosphaera leucotricha; Venturia species, such as, forexample, Venturia inaequalis; Pyrenophora species, such as, for example,Pyrenophora teres or P. graminea (conidia form: Drechslera, syn:Helminthosporium); Cochliobolus species, such as, for example,Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as, for example, Uromyces appendiculatus;Puccinia species, such as, for example, Puccinia recondita; Tilletiaspecies, such as, for example, Tilletia caries; Ustilago species, suchas, for example, Ustilago nuda or Ustilago avenae; Pellicularia species,such as, for example, Pellicularia sasakii; Pyricularia species, suchas, for example, Pyricularia oryzae; Fusarium species, such as, forexample, Fusarium culmorum; Botrytis species, such as, for example,Botrytis cinerea; Septoria species, such as, for example, Septorianodorum; Leptosphaeria species, such as, for example, Leptosphaerianodorum; Cercospora species, such as, for example, Cercospora canescens;Alternaria species, such as, for example, Alternaria brassicae andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can be used withparticularly good success here for combating cereal diseases, such as,for example, against the brown glume of wheat causative organism(Leptosphaeria nodorum) or against the leaf spot disease of barleycausative organism (Pyrenophora teres) or against the leaf spot diseaseof wheat causative organism (Cochliobolus sativus) and against powderymildew and rust species, or for combating diseases in fruit andvegetable growing, such as, for example, against the apple scabcausative organism (Venturia inaequalis) equalis) and againstPhytophthora and Botrytis species, or for combating diseases in ricegrowing, such as, for (Pyricularia oryzae).

The active compounds according to the invention moreover exhibit a goodinsecticidal activity, for example against leaf aphids (Myzus persicae)and plant growth-regulating properties.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV cold mist and warm mistformulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andsawdust, coconut shells, oorn cobs and tobacco stalks; as emulsifyingand/or foam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethyleOe-fatty acid esters,polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and cyntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and in mixtureswith fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, wettable powders, pastes,soluble powders, dusts and granules. They are used in the customarymanner, for example by watering, spraying, atomizing, scattering,dusting, foaming, brushing on and the like. It is furthermore possibleto apply the active compounds by the ultra-low volume method or toinject the active compound formulation or the active compound itselfinto the soil. The seed of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

The active compounds according to the invention can also be used in thepreservation of materials for preservation of industrial materials.

According to the invention, industrial materials are nonliving materialswhich have been prepared for use in industry. For example, industrialmaterials which are to be protected by active compounds according to theinvention from microbial change or destruction can be adhesives, sizes,paper and card, textiles, leather, wood, paints and articles made ofplastic, cooling lubricants and other materials which can be attacked ordecomposed by microorganisms. Components of production lines, forexample cooling water circulations, which can be impaired bymultiplication of micro-organisms may also be mentioned in the contextof materials to be preserved. Adhesives, sizes, paper and card, leather,wood, paints, cooling lubricants and cooling circulations may bementioned as preferred

Examples which may be mentioned of micro-organisms which can causedegradation or a change in industrial materials are bacteria, fungi,yeasts, algae and slime organisms. The active compounds according to theinvention preferably act against fungi, in particular molds andwood-discoloring and wood-destroying fungi (Ba$idiomycetes), and againstslime organisms and algae.

Micro-organisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puteana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trihoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeroginosa, and

Staphylococcus, such as Staphylococcus aureus.

An active compound can be converted into the customary formulationsaccording to the field of use, such as solutions, emulsions,suspensions, powders, pastes and granules.

These can be prepared in a manner which is known per se, for example bymixing the active compounds with an extender consisting of a liquidsolvent and/or solid carriers, if appropriate using surface-activeagents, such as emulsifiers and/or dispersing agents, and ifappropriate, in the case where water is used as an extender, organicsolvents, such as alcohols, can be used as auxiliaries.

Liquid solvents for the active compounds can be, for example, water,alcohols, such as lower aliphatic alcohols, preferably ethanol orisopropanol, or benzyl alcohol, ketones, such as acetone or methyl ethylketone, liquid hydrocarbons, such as benzine fractions, or halogenatedhydrocarbons, such as 1,2-dichloroethane.

Microbicidal agents in general contain the active compounds in an amountof 1 to 95%, preferably 10 to 75%.

The use concentrations of the active compounds according to theinvention depend on the nature and occurrence of the micro-organisms tobe combated and on the composition of the material to be preserved. Theoptimum amount to be used can be determined by test series. In general,the use concentrations are in the range from 0.001 to 5% by weight,preferably 0.05 to 1.0% by weight, based on the material to bepreserved.

The active compounds according to the invention can also be as a mixturewith other known active compounds. The following active compounds may bementioned as examples: benzyl alcohol mono(poly)hemiformal and othercompounds which split off formaldehyde, benzimidazolyl methylcarbamates,tetramethylthiuram disulphide, zinc salts of dialkyldithiocarbamates,2,4,5,6-tetrachloroisophthalonitrile, thiazolylbenzimidazole,mercaptobenzothiazole, organotin compounds, methylenebisthiocyanate andphenol derivatives, such as 2-phenylphenol,(2,2'-dihydroxy-5,5'-dichloro)diphenylmethane and3-methyl-4-chloro-phenol.

PREPARATION EXAMPLES Example 1 ##STR44##

24.7 g (0.1 mol) of 8-s-butyl-2-chloromethyl-1,4dioxaspiro [4,5] decaneand 45.2 g (0.4 mol) of cis-3,5-dimethylpiperidine are stirred at 140°C. for 16 hours and cooled, 200 ml of ethyl acetate are added, themixture is washed three times with 200 ml of water each time, dried oversodium sulphate and concentrated in vacuo and the residue is purified bychromatography (silica gel; mobile phase: ethyl acetate). 24.3 g (75% oftheory) of 8-s-butyl-2-(3,5-dimethylpiperidin-1-ylmethyl)-1,4-dioxaspiro[4,5] decane are obtained as an oil of refractive indexn_(d) ²⁰ 1.4762.

PREPARATION OF THE STARTING COMPOUNDS Example II-1 ##STR45##

83.7 mL (1 mol) of 3-chloropropane-1,2-diol and 9.5 g (0.05 mol) ofp-toluenesulphonic acid are added to 77 g (0.5 mol) of4-s-butylcyclohexanone in 1,000 ml of toluene, the mixture is heatedunder reflux for 16 hours, using a water separator, cooled, washed threetimes with 1,000 ml of saturated aqueous sodium bicarbonate solutioneach time, dried over sodium sulphate and concentrated in vacuo and theresidue is dried under a high vacuum.

120.4 g (98% of theory) of 8-s-butyl-2-chloromethyl-1,4dioxaspiro[4,5]decane are obtained as an oil of refractive index n_(d) ²⁰ 1.4776

Example V-a ##STR46## 156 g (1 mol) of 4-s-butyl-cyclohexanol are addedto a solution of 106.6 g (0.4 mol) of sodium dichromate in 812 ml ofwater, 92.9 ml of concentrated sulphuric acid are then added dropwise at70° C., the mixture is allowed to cool to room temperature and isextracted four times with 500 ml of ethyl acetate each time, thecombined organic phases are washed twice with 500 ml of 5% strengthsodium hydroxide solution each time and once with 500 ml of water anddried over sodium sulphate and the solvent is then removed in vacuo.

131.3 g (85% of theory) of 4-s-butylcyclohexanone of refractive indexn_(D) ²⁰ 1.3547 are obtained. ##STR47##

20 g of ruthenium (5% strength on active charcoal) are added to 200 g(1.33 mols) of 4-s-butylphenol (compare, for example, U.S. Pat. No.3,418,379) in 200 ml of isopropanol and the mixture is hydrogenated inan autoclave at 150° C. under a hydrogen pressure of 200 bar. Forworking up, the catalyst is filtered off and the solvent is distilledoff.

193.4 g (93% of theory) of 4-s-butylcyclohexanol are obtained as an oilof refractive index n_(D) ²⁰ 1.4660.

The following aminomethylheterocyclic compounds of the general formula(I) are obtained in a corresponding manner and in accordance with thegeneral instructions for the preparation:

    __________________________________________________________________________     ##STR48##                                   (I)                               Example No.                                                                          X                                                                               R                                                                                          ##STR49##    Physical properties                       __________________________________________________________________________    2      O                                                                                ##STR50##                                                                                  ##STR51##   n.sub.D.sup.20 1.5275                      3      O                                                                                ##STR52##                                                                                  ##STR53##   n.sub.D.sup.20 1.5214                      4      O                                                                                ##STR54##                                                                                  ##STR55##   n.sub.D.sup.20 1.5289                      5      O                                                                                ##STR56##                                                                                  ##STR57##   n.sub.D.sup.20 1.5165                      6      O                                                                                ##STR58##                                                                                  ##STR59##   n.sub.D.sup.20 1.5304                      7      O                                                                                ##STR60##                                                                                  ##STR61##   n.sub.D.sup.20 1.5181                      8      O                                                                                ##STR62##                                                                                  ##STR63##   n.sub.D.sup.20 1.4974                      9      O                                                                                ##STR64##                                                                                  ##STR65##   n.sub.D.sup.20 1.4935                      10     O                                                                                ##STR66##                                                                                  ##STR67##   n.sub.D.sup.20 1.4997                      11     O                                                                                ##STR68##                                                                                  ##STR69##   n.sub.D.sup.20 1.4909                      12     O                                                                                ##STR70##                                                                                  ##STR71##   n.sub.D.sup.20 1.4972                      13     O                                                                                ##STR72##                                                                                  ##STR73##   n.sub.D.sup.20 1.4901                      14     O                                                                                ##STR74##                                                                                  ##STR75##   n.sub.D.sup.20 1.5113                      15     O                                                                                ##STR76##                                                                                  ##STR77##   n.sub.D.sup.20 1.4828                      16     O                                                                                ##STR78##                                                                                  ##STR79##   n.sub.D.sup.20 1.4969                      17     O                                                                                ##STR80##                                                                                  ##STR81##   n.sub.D.sup.20 1.4929                      18     O                                                                                ##STR82##                                                                                  ##STR83##   n.sub.D.sup.20 1.4841                      19     O                                                                                ##STR84##                                                                                  ##STR85##   n.sub.D.sup.20 1.4868                      20     O                                                                                ##STR86##                                                                                  ##STR87##   n.sub.D.sup.20 1.4925                      21     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR88##   n.sub.D.sup.20 1.4790                      22     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR89##   n.sub.D.sup.20 1.4764                      23     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR90##   n.sub.D.sup.20 1.4729                      24     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR91##   n.sub.D.sup.20 1.4746                      25     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR92##   .sup.1 H-NMR*: 3.5-3.68(m,3H); 4.1-4.3                                        (m,1H); 4.6-4.75(m,1H) (salt with                                             saccharin)                                 26     O H.sub.3 C(CH.sub.2).sub.2                                                                   ##STR93##   .sup.1 H-NMR*: 3.4-3.9 (m,3H);                                                4.05-4.2(m,1H); 4.6-4.75(m,1H) (salt                                          with p-dodecyl- benzene-sulphonic                                             acid)                                      27     O                                                                                ##STR94##                                                                                  ##STR95##   n.sub.D.sup.20 1.4816                      28     O                                                                                ##STR96##                                                                                  ##STR97##   n.sub.D.sup.20 1.4795                      29     O                                                                                ##STR98##                                                                                  ##STR99##   n.sub.D.sup.20 1.4866                      30     O                                                                                ##STR100##                                                                                 ##STR101##  n.sub.D.sup.20 1.4826                      31     O                                                                                ##STR102##                                                                                 ##STR103##  n.sub.D.sup.20 1.4775                      32     O                                                                                ##STR104##  NHC.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1.4869                      33     O                                                                                ##STR105##                                                                                 ##STR106##  n.sub.D.sup.20 1.5110                      34     O                                                                                ##STR107##                                                                                 ##STR108##  n.sub.D.sup.20 1.5085                      35     O                                                                                ##STR109##                                                                                 ##STR110##  n.sub.D.sup.20 1.5086                      36     O                                                                                ##STR111##                                                                                 ##STR112##  n.sub.D.sup.20 1.5067                      37     O                                                                                ##STR113##                                                                                 ##STR114##  n.sub.D.sup.20 1.4821                      38     O                                                                                ##STR115##                                                                                 ##STR116##  n.sub.D.sup.20 1.4825                      39     O                                                                                ##STR117##                                                                                 ##STR118##  n.sub.D.sup.20 1.5254                      40     O                                                                                ##STR119##                                                                                 ##STR120##  n.sub.D.sup.20 1.5211                      41     O                                                                                ##STR121##                                                                                 ##STR122##  n.sub.D.sup.20 1.5174                      42     O                                                                                ##STR123##                                                                                 ##STR124##  .sup.1 H-NMR*: 3.1-3.4 (m,2H);                                                3.75-3.85(m,2H)                            43     O                                                                                ##STR125##                                                                                 ##STR126##  .sup.1 H-NMR*: 3.1-3.4(m,2H); 3.7-3.9(m                                       ,2H);                                      44     O                                                                                ##STR127##                                                                                 ##STR128##  .sup.1 H-NMR*: 3.5-3.9(m,2H); 3.95-4.05                                       (m,1H)                                     45     O                                                                                ##STR129##                                                                                 ##STR130##  .sup.1 H-NMR*: 3.5-3.9(m,2H); 4.0-4.1(m                                       ,1H)                                       46     O                                                                                ##STR131##  NH(CH.sub.2).sub.3CH.sub.3                                                                 n.sub.D.sup.20 1.5145                      47     O                                                                                ##STR132##                                                                                 ##STR133##  n.sub.D.sup.20 1.5049                      48     O                                                                                ##STR134##                                                                                 ##STR135##  n.sub.D.sup.20 1.5031                      49     O                                                                                ##STR136##                                                                                 ##STR137##  .sup.1 H-NMR*: 3.4-3.7(m,2H); 4.0-4.15(                                       m,1H)                                      50     O                                                                                ##STR138##                                                                                 ##STR139##  .sup.1 H-NMR*: 3.5-3.6(m,2H); 4.0-4.1(m                                       ,1H) (Diastereo- mer A)                    51     O                                                                                ##STR140##                                                                                 ##STR141##  .sup.1 H-NMR*: 3.55-3.65(m,2H);                                               4.0-4.1(m,1H) (Diastereo- mer B)           52     O                                                                                ##STR142##                                                                                 ##STR143##  .sup.1 H-NMR*: 3.4-3.8(m,2H); 3.95-4.1(                                       m,1H)                                      53     O                                                                                ##STR144##                                                                                 ##STR145##  .sup.1 H-NMR*: 3.6-3.8(m,1H) 3.9-4.15(m                                       ,2H)                                       54     O                                                                                ##STR146##                                                                                 ##STR147##  .sup.1 H-NMR*: 3.4-3.7(m,2H); 3.95-4.1(                                       m,1H)                                      55     O                                                                                ##STR148##                                                                                 ##STR149##  .sup.1 H-NMR*: 3.45-3.7(m,2H);                                                3.95-4.1(m,1H)                             56     O                                                                                ##STR150##                                                                                 ##STR151##  n.sub.D.sup.20 1.4909 (Diastereo- mer                                         A)                                         57     O                                                                                ##STR152##                                                                                 ##STR153##   n.sub.D.sup.20 1.4884 (Diastereo- mer                                        B)                                         58     O                                                                                ##STR154##                                                                                 ##STR155##  n.sub.D.sup.20 1.5370                      59     O                                                                                ##STR156##                                                                                 ##STR157##  n.sub.D.sup.20 1.5413                      60     O                                                                                ##STR158##                                                                                 ##STR159##  .sup.1 H-NMR*: 3.65-3.75(m,1H);                                               4.0-4.2(m,2H)                              61     O                                                                                ##STR160##                                                                                 ##STR161##  .sup.1 H-NMR*: 3.65-3.8(m,1H);                                                4.0-4.25(m,2H)                             62     O                                                                                ##STR162##  NH(CH.sub.2).sub.2CH.sub.3                                                                 bp 120° C./ 0.5 mbar                63     O                                                                                ##STR163##  NH(CH.sub.2).sub.2OCH.sub.3                                                                bp 125° C./ 0.5 mbar                64     O                                                                                ##STR164##                                                                                 ##STR165##  n.sub.D.sup.20 1.4837                      65     O                                                                                ##STR166##                                                                                 ##STR167##  n.sub.D.sup.20 1.4805                      66     O                                                                                ##STR168##                                                                                 ##STR169##  n.sub.D.sup.20 1.4851                      67     O                                                                                ##STR170##                                                                                 ##STR171##  n.sub.D.sup.20 1.4793                      68     O                                                                                ##STR172##                                                                                 ##STR173##  n.sub.D.sup.20 1.4797                      69     S                                                                                ##STR174##                                                                                 ##STR175##  mp: 29-31° C.                       70     S                                                                                ##STR176##                                                                                 ##STR177##  mp: 34-36° C.                       71     S                                                                                ##STR178##                                                                                 ##STR179##  mp: 38° C.                          72     S                                                                                ##STR180##                                                                                 ##STR181##  n.sub.D.sup.20 1.5462                      73     S                                                                                ##STR182##                                                                                 ##STR183##  n.sub.D.sup.20 1.5514                      74     S                                                                                ##STR184##                                                                                 ##STR185##  n.sub.D.sup.20 1.5364                      75     S                                                                                ##STR186##  NH(CH.sub.2).sub.3OC.sub.2 H.sub.5                                                         n.sub.D.sup.20 1.5329                      76     S                                                                                ##STR187##                                                                                 ##STR188##  n.sub.D.sup.20 1.5591 (salt with                                              saccharin)                                 77     S                                                                                ##STR189##                                                                                 ##STR190##  n.sub.D.sup.20 1.5600 (salt with                                              saccharin)                                 78     S                                                                                ##STR191##                                                                                 ##STR192##  n.sub.D.sup.20 1.5452 (salt with                                              saccharin)                                 79     S                                                                                ##STR193##                                                                                 ##STR194##  n.sub.D.sup.20 1.5509 (salt with                                              saccharin)                                 80     S                                                                                ##STR195##                                                                                 ##STR196##  n.sub.D.sup.20 1.5539                      81     S                                                                                ##STR197##                                                                                 ##STR198##  n.sub.D.sup.20 1.5440                      82     S                                                                                ##STR199##                                                                                 ##STR200##  n.sub.D.sup.20 1.5538                      83     S                                                                                ##STR201##                                                                                 ##STR202##  .sup.1 H-NMR*: 4.3-4.55(m,1H) 3.0-3.2                                         (m,2H)                                     84     S                                                                                ##STR203##                                                                                 ##STR204##  4.25-4.5(m,1H) 3.05-3.15(m,1H) 2.6-3.0                                        (m,7H)                                     85     S                                                                                ##STR205##                                                                                 ##STR206##  n.sub.D.sup.20 1.5346                      86     S                                                                                ##STR207##  NHCH.sub.2CH(CH.sub.3).sub.2                                                               n.sub.D.sup.20 1.5269                      87     S                                                                                ##STR208##  NHCH.sub.2CH(C.sub.2 H.sub.5).sub.2                                                        n.sub.D.sup.20 1.5074                      88     S                                                                                ##STR209##                                                                                 ##STR210##  .sup.1 H-NMR*: 4.65-4.9(m,1H) 3.9-4.15(                                       m,4H) 3.05-3.65(m,4H) (salt with                                              saccharin)                                 89     S                                                                                ##STR211##                                                                                 ##STR212##  n.sub.D.sup.20 1.5141                      90     S                                                                                ##STR213##                                                                                 ##STR214##  n.sub.D.sup.20 1.4990                      91     S                                                                                ##STR215##                                                                                 ##STR216##  n.sub.D.sup.20 1.5232                      92     S                                                                                ##STR217##  NH(CH.sub.2).sub.2OCH.sub.3                                                                n.sub.D.sup.20 1.5948                      93     S                                                                                ##STR218##                                                                                 ##STR219##  n.sub.D.sup.20  1.5068                     94     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR220##  n.sub.D.sup.20 1.4635                      95     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR221##  n.sub.D.sup.20 1.4640                      96     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR222##  n.sub.D.sup.20 1.4640                      97     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR223##  n.sub.D.sup.20 1.4619                      98     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR224##  n.sub.D.sup.20 1.4633                      99     O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR225##  n.sub.D.sup.20 1.4629                      100    O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR226##  n.sub.D.sup.20 1.4635                      101    O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR227##  n.sub.D.sup.20 1.4645                      102    O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 ##STR228##  n.sub.D.sup.20 1.4637                      103    O                                                                                ##STR229##                                                                                 ##STR230##  n.sub.D.sup.20 1.4794                      104    O                                                                                ##STR231##                                                                                 ##STR232##  n.sub.D.sup.20 1.4789                      105    O                                                                                ##STR233##                                                                                 ##STR234##  n.sub.D.sup.20 1.4775                      106    O                                                                                ##STR235##                                                                                 ##STR236##  n.sub.D.sup.20 1.4772                      107    O                                                                                ##STR237##                                                                                 ##STR238##  n.sub.D.sup.20 1.4757                      108    O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 ##STR239##  n.sub.D.sup.20 1.4816                      109    O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 ##STR240##  n.sub.D.sup.20 1.4821                      110    O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 ##STR241##  n.sub.D.sup.20 1.4782                      111    O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 ##STR242##  n.sub.D.sup.20 1.4757                      112    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR243##  n.sub.D.sup.20 1.4832                      113    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR244##  n.sub.D.sup.20 1.4810                      114    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR245##  n.sub.D.sup.20 1.4792                      115    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR246##  n.sub.D.sup.20 1.4766                      116    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR247##  n.sub.D.sup.20 1.4863                      117    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR248##  n.sub.D.sup.20 1.4857                      118    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR249##  n.sub.D.sup.20 1.4825                      119    O CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub. 2                                                    ##STR250##  n.sub.D.sup.20 1.4799                      120    O CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2                                                     ##STR251##  n.sub.D.sup.20 1.4769                      121    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR252##  n.sub.D.sup.20 1,3890                      122    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR253##  n.sub.D.sup.20 1.4808                      123    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR254##  n.sub.D.sup.20 1.4805                      124    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                         NH(CH.sub.2).sub.2 OCH.sub.3                                                               n.sub.D.sup.20 1.4707                      125    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                         NH(CH.sub.2).sub.2 CH.sub.3                                                                n.sub.D.sup.20 1,4687                      126    O CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2                                                    NH(CH.sub.2).sub.2 CH.sub.3                                                                n.sub.D.sup.20 1.4659                      127    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR255##  n.sub.D.sup.20 1.4767                      128    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR256##  n.sub.D.sup.20 1.4759                      129    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR257##  n.sub.D.sup.20 1,4855                      130    O CH(CH.sub.3)C.sub.5 H.sub.11                                                                ##STR258##  n.sub.D.sup.20 1.4813                      131    O CH(CH.sub.3)C.sub.5 H.sub.11                                                               NHC.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1,4525                      132    O CH(CH.sub.3)C.sub.5 H.sub.11                                                               NH(CH.sub.2).sub.2 CH.sub.3                                                                n.sub.D.sup.20 1.4669                      133    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR259##  n.sub.D.sup.20 1.4623                      134    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR260##  n.sub.D.sup.20 1.4636                      135    O CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2                                                     ##STR261##  n.sub.D.sup.20 1.4642                      136    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR262##  n.sub.D.sup.20 1.4675                      137    O CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                                                          ##STR263##  n.sub.D.sup.20 1.4670                      138    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR264##  n.sub.D.sup.20 1.4869                      139    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR265##  n.sub.D.sup. 20 1.4817                     140    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR266##  n.sub.D.sup.20 1.4834                      141    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                               NHC.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1,4657                      142    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                               NH(CH.sub.2).sub.2 OCH.sub.3                                                               n.sub.D.sup.20 1.4677                      143    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                               NH(CH.sub.2).sub.2 CH.sub.3                                                                n.sub.D.sup.20 1.4674                      144    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR267##  n.sub.D.sup.20 1.4653                      145    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR268##  n.sub.D.sup.20 1.4647                      146    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR269##  n.sub.D.sup.20 1.4633                      147    O CH(CH.sub. 3)C.sub.5 H.sub.11                                                               ##STR270##  n.sub.D.sup.20 1.4657                      148    O CH(CH.sub. 3)C.sub.3 H.sub.7                                                                ##STR271##  n.sub.D.sup.20 1.4652                      149    O CH(CH.sub. 3)C.sub.5 H.sub.11                                                               ##STR272##  n.sub.D.sup.20 1.4644                      150    O CH(CH.sub. 3)C.sub.5 H.sub.11                                                               ##STR273##  n.sub.D.sup.20 1.4641                      151    O CH(CH.sub. 3)C.sub.5 H.sub.11                                                               ##STR274##  n.sub.D.sup.20 1.4655                      152    O                                                                                ##STR275##                                                                                 ##STR276##  Oil                                        153    O                                                                                ##STR277##                                                                                 ##STR278##  Oil                                        154    O                                                                                ##STR279##                                                                                 ##STR280##  Oil (diastereom. A)                        155    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR281##  n.sub.D.sup.20 1.4814                      156    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR282##  n.sub.D.sup.20 1.4846                      157    O CH(C.sub.3 H.sub.7).sub.2                                                                  NHC.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.4664                      158    O CH(C.sub.3 H.sub.7).sub.2                                                                  NH(CH.sub.2).sub.2 OCH.sub.3                                                               n.sub.D.sup.20 1.4659                      159    O CH(C.sub.2 H.sub.5).sub.2                                                                  NHC.sub.5 H.sub.11                                                                         n.sub.D.sup.20 1.4689                      160    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR283##  n.sub.D.sup.20 1.4786                      161    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR284##  n.sub.D.sup.20 1.4773                      162    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR285##  n.sub.D.sup.20 1.4768                      163    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR286##  n.sub.D.sup.20 1.4854                      164    O CH(C.sub.3 H.sub.7).sub.2                                                                   ##STR287##  n.sub.D.sup.20 1.4814                      __________________________________________________________________________     *The .sup.1 HNMR spectra were recorded in deuterochloroform (CDCl.sub.3)      using tetramethylsilane (TMS) as the internal standard. The chemical shif     is stated as the δ value in ppm.              *) The .sup.1 H-NMR       spectra were recorded in deuterochloroform (CDCl.sub.3) using     tetramethylsilane (TMS) as the internal standard. The chemical shift is     stated as the δ value in ppm.

USE EXAMPLES

The compounds shown below wee employed as comparison substances in theuse examples which follow: ##STR288##

EXAMPLE A Leptosphaeria nodorum test (wheat)/protective/

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 48 hours. The plants areplaced in a greenhouse at a temperature of about 15° C. and a relativeatmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, for example, a clearly superior activity compared with theprior art is shown, for example, by the compounds according toPreparation Examples 3, 8, 9, 10, 14, 26, 27, 28, 29, 39, 40, 41, 44,45, 46, 47, 48, 52, 55, 70, 72, 75 and 85.

EXAMPLE B Cochliobolus sativus test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofCochliobolus sativus. The plants remain in an incubation cabin at 20° C.and 100% relative atmospheric humidity for 48 hours. The plants areplaced in a greenhouse at a temperature of about 20° C. and a relativeatmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, a clearly superior activity compared with theprior art is shown, for example, by the compounds according toPreparation Examples 39, 40, 41, 42, 44, 45, 55, 72, 75 and 85.

EXAMPLE C

Venluria tesl (apple)/protective

Solvent: 4.7 parls by weight of acetone

Emulsifier: 0parls by weighl of alkylaryl poIyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples 40 and 41.

EXAMPLE D

The compounds according to the invention were incorporated in graduatedconcentrations of between 1 and 5,000 mg/1 of test samples into an agarprepared from beer wort and peptone. After the agar had solidified, theagar samples thus prepared were contaminated with pure cultures ofvarious test fungi.

After storage at 28° C. and 60 to 70% relative atmospheric humidity fortwo weeks, the experiment was evaluated. The minimum concentration ofsubstance contained in an agar sample at which no growth at all of thespecies used took place is stated as the minimum inhibitoryconcentration (MIC) in the table.

In this test, for example, compounds 52, 53, 15, 9 and 10 exhibit a verygood action.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. An aminomethylheterocyclic compound of the formula##STR289## wherein R represents cycloalkyl having 3 to 7 carbon atoms,or represents aryl which has 6 to 10 carbon atoms and is optionallysubstituted by one or more identical or different straight-chain orbranched alkyl radicals having 1 to 12 carbon atoms, or represents theradical ##STR290## R¹ and R² independently of one another each representhydrogen, or represent in each case straight-chain or branched alyylhaving 1 to 12 carbon atoms, allkenyl having 3 to 8 carbon atoms,alkynyl having 3 to 8 carbon atoms, hydroxyalkyl having 2 to 6 carbonatoms, alkoxyalkyl or dialkoxyalky having in each case 1 to 6 carbonatoms or hydoxyalkoxyalkyl having 2 to 6 carbon atoms in the individualalkyl parts,or represent alkoxycarbonylalky having 1 to 6 carbon atomsper alkoxy and alkyl part, or represent in each case straight-chain orbranched dioxolanylalkyl, dioxanylalkyl or oxolanylalkyl having in eachcase 1 to 4 carbon atoms int he alkyl part, or represent cycloalkyl orcycloalkylalkyl having in each case 3 to 7 carbon atoms in thecycloalkyl part and if appropriate 1 to 4 carbon atoms in thestraight-chain or branched alkyl part and in each case optionallysubstituted in the cycloalkyl part by one or more identical or differentsubstituents selected fromt eh group consisting of halogen and in eachcase straight-chain or branched alkyl, alkoxy, halogenoalkyl andhalogenoalkoxy having in each case 1 to 4 carbon atoms and ifappropriate 1 to 9 identical or different halogen atoms; or in additonrepresent arylalkyl, arylalkenyl or aryl having in each case 6 to 10carbon atoms in the aryl part and if appropriate up to 6 carbon atoms inthe straight-chain or branched alkyl or alkenyl part and in each caseoptionally substituted in the aryl part by one or more identical ordiffernt substituents selected from the group consisting of halogen,cyano, nitro and in each case straight-chain or branched alkyl, alkoxy,alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio,alkoxycarbonyl and alkoximinoalkyl having in each case 1 to 4 carbonatoms in the individual alkyl parts and if approprite 1 to 9 identicalor different halogen atomsR³ represents hydrogen, or representsstraight-chain or branched alkyl having 1 to 12 carbon atoms, orrepresents aryl which has 6 to 10 carbon atoms and is optionallysubstitued by one or more identical or differnt straight-chain orbranched alkyl radicals having 1 to 12 carbon atoms, and R⁴ representsstraight-chain or branched alkyl having 1 to 12 carbon atoms, orrepresents cycloalkyl having 3 to 7 carbon atoms, or represents arylwhich has 6 to 10 carbon atoms and is optionally substituted by one ormore identical or different straight-chain or branched alkyl radicalshaving 1 to 12 carbon atoms, but wherein R³ and R⁴ may notsimultaneously represent methyl,or an acid addition salt thereof.
 2. Anaminomethylheterocyclic compound or salt thereof according to claim 1,whereinR represents cyclopentyl or cyclohexyl, or represents phenylwhich is optionally substituted by one to three identical or differentsubstituents from the group consisting of methyl, ethyl, n- or i-proplyand n-, i-, s-, or t-butyl, or represents a radical ##STR291## R¹ and R²independently of one another each represent hydrogen methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n-ori-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl,propargyl, n- or i-butynyl, hydroxyethyl, hydroxypropyl, butoxyethyl,methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl,hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl,methoxycarbonylmethyl, oxycarbonylmethyl, methoxycarbonylethyl,methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl,ethoxycarbonylpropyl, propoxycarbonylemehyl, proproxycarbonylethyl,propoxycarbonylpropyl, dioxolanylmethyl, propoxycarbonylmethyl,propoxycarbonylethyl, propoxycarbonylpropyl, dioxolanylmethyl,dioxolanylethyl, dioxanylmethyl, dioxanylethyl, oxolanylmethyl oroxolanylethyl, or represent cyclopropyl, cyclopropylmethyl,cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl,cyclohexyl or cyclohexylmethyl, in each case optionally substituted byone to five identical or different substituents from the group fluorine,chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,trifluoromethyl and trifluoromethoxy, or represent phenyl, benzyl orphenethyl, in each case optionally substituted by one to three identicalor different substituents selected from the group consisting offluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl,ethoxycarbonyland methoximinomethyl, or R³ represents hydrogen, methyl,ethyl or n- or i-propyl, or represents in each case straight-chain orbranched butyl, pentyl or hexyl, or represents phenyl which isoptionally substituted by one to three identical or differentsubstituents from the group consisting of methyl, ethyl, n- or i-propyland n-, i-, s- or t-butyl, and R⁴ represents methyl, ethyl or n- ori-propyl, or represents in each case straight-chain or branched butyl,pentyl or hexyl, or represents cyclopentyl or cyclohexyl, or representsphenyl which is optionally substituted by one to three identical ordifferent substituents from the group oonsisting of methyI, ethyl, n-ori-propyl and n-, i-, s- or t-butyl,but wherein R³ and R⁴ may notsimultaneously represent methyl.
 3. An aminomethylhetarocyclic compoundor salt thereof according to claim 2, whereinR represents cyclohexyl, orrepresents phyenyl, or represents a radical ##STR292## R¹ and R²independently of one another reach represent hydrogen, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl,n-or i-butenyl, n- or i- pententyl, propargyl, n- or i-butynyl,hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ehtoxyethyl,ethoxypropyl, hyroxyethoxyethyl, dimenthoxyethyl, diethoxyethyl,methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl,ethoxycarbonylemthyl, ethoxycarbonylethyl, ethoxycarbonylproply.propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl,dioxolanylmehtyl, dioxolanylethyl, dioxanylemethyl, oxolanymethyl,oxolanylethhyl, cycolpropylemhyl, dichlorocyclopropylmethyl,dimethylcycoprppylmethyl, dichlorodimethylcyclopropylmethyl,cycolopentyl, cyclohexyl or cyclohexylmethyl, R³ represents hydrogen,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or phenyl, and R⁴represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, orrpresents cyclohexyl, or represents phenyl,but wherin R³ and R⁴ may notsimultaneously represent methyl.
 4. A compound according to claim 1,wherein such compound is 8-phenyl-2-(-b3-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5] decane of theformula ##STR293## or an acid addition salt thereof.
 5. A compoundaccording to claim 1, wherein such compound is 8-phenyl-2-(-b4-methylcyclohexylaminomethyl)-1,4-dioxasiro [4,5] decane of the formula##STR294## or an acid addition salt thereof.
 6. A compound according toclaim 1, wherein such compound is8-phenyl-2-(n-butylaminomethyl)-1,4-dioxaspiro [4,5] ##STR295## or anacid addition salt thereof.
 7. A compound according to claim 1, whereinsuch compound is8-(but-2-yl)-2-(3-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5]decane of the formula ##STR296## or an acid addition salt thereof.
 8. Acompound according to claim 1, wherein such compound is8-(but-2-yl)-2-(2-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5]decane of the formula ##STR297## or an acid addition salt thereof.
 9. Acompound according to claim 1, wherein such compound is8-(but-2-yl)-2-(4-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5]decane of the formula ##STR298## or an acid addition salt thereof.
 10. Acompound according to claim 1, wherein such compound is8-(but-2-yl)-2-(N-ethyl-N-n-butyl-aminomethyl)-1,4-dioxaspiro [4,5]decane of the formula ##STR299## or an acid addition salt thereof.
 11. Afungicidal composition comprising a fungicidally effective amount of acompound or salt thereof according to claim 1 and an inert diluent. 12.A method of combating fungi which comprises applying to such fungi or toa fungus habitat a fungicidally effective amount of a compound or salttherof according to claim
 1. 13. The method according to claim 12,wherein such compoundis8-phenyl-2-(4-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5]decane, 8-phenyl-2-(4-methylcyclohexylaminomethyl)-1,4-dioxaspiro[4,5]decane, or 8-phenyl-2-(n-butylaminomethyl)-1,4-dioxaspiro [4,5] decane,8-(but-2-yl)-2-(3-methylcyclohexylaminomethyl)-1,4dioxasiro [4,5]decane, 8-(but-2-yl)-2-(-2methylcyclohexylaminomethyl)-1,4-dioxaspiro[4,5] decane,8-(but-2-yl)-2-(4-methylcyclohexylaminomethyl)-1,4-dioxaspiro [4,5]decane, or 8-(but-2-yl)-2-(N-ethyl-N-n-butyl-aminomethyl)-1,4-dioxaspiro[4,5] decane.